JP5566510B2 - Episulfide compound curing agent, curable composition, episulfide compound cured product, and episulfide compound curing method - Google Patents

Description

  The present invention relates to a curing agent for an episulfide compound, a curable composition, and a cured product of an episulfide compound, and in particular, a photobase generating type curing agent for an episulfide compound, and a curable composition containing such a curing agent and an episulfide compound. The present invention relates to a cured product of an episulfide compound cured by such a curing agent. Furthermore, the present invention relates to a curing method for curing an episulfide compound with such a curing agent.

  A cured resin obtained by curing an episulfide compound with a curing agent is excellent in heat resistance, moisture resistance, transparency, refractive index, etc. Application development is possible. In particular, it can be advantageously used in applications such as electrical materials such as semiconductor sealing materials and electrical insulation materials, and optical materials such as lens resins.

As a curing agent for an episulfide compound, for example, a curing agent for an anion curable compound such as 1,3-bis (aminomethyl) cyclohexane or 1,8-diazabicyclo [5.4.0] -7-undecene is generally used. Basic compounds are used.
However, since the reactivity is very high, the storage stability of the curable composition containing the episulfide compound and the curing agent is poor, and there is a problem that the pot life is very short. Therefore, the use of a base generator has been proposed as a means for allowing the curing reaction to be carried out quickly by external stimulation, and the storage stability of the curable composition is good.

As a base generator, the photobase generator of patent document 1 is mentioned, for example.
However, the photobase generator of Patent Document 1 is limited in the base that can be generated, and it is difficult to adjust the base strength. In addition, the base generation efficiency by the action of light is low, and there is also a disadvantage that the reaction for generating the base is difficult to be performed quickly.

  On the other hand, a base generator having high base generation efficiency is disclosed in, for example, Patent Document 2. However, since this base generator is accompanied by a decarboxylation reaction when generating a base by light irradiation, outgas is also generated at the same time. Therefore, the generated outgas may remain as bubbles in the cured film, and in that case, the strength of the cured film may be reduced.

  Then, the photobase generator which does not generate an outgas is disclosed by patent document 3, for example. However, even in this photobase generator, the base generation efficiency is still not satisfactory for the recently required high performance, and further improvement of the photobase generator is required.

JP 2005-264156 A JP 2009-280785 A JP 2009-80452 A

  In the present invention, under such a background, the base generation efficiency is excellent, the outgassing does not occur, and further the photobase generation type curing agent for episulfide compound excellent in storage stability when used as a curable composition, It aims at providing the curable composition containing this hardening | curing agent and an episulfide compound, the hardened | cured material of the episulfide compound hardened | cured with this hardening | curing agent, and also the hardening method.

  However, as a result of intensive studies in view of such circumstances, the present inventors can generate a base more efficiently than a conventional photobase generator by using a compound represented by the following general formula (1). Further, the present inventors have found that no outgassing is involved in curing the episulfide compound and that the curable composition containing the curing agent and the episulfide compound has good storage stability.

  That is, the gist of the present invention is an episulfide compound curing agent comprising the compound represented by the following general formula (1).

In general formula (1),
X ₁ , X ₂ , and X ₃ are each independently any one selected from the group consisting of a hydrogen atom, an oxygen atom, an alkylene group having 1 to 3 carbon atoms, a sulfur atom, a sulfonyl group, and a silanol group. An atom or group.
R1, R2, and R3 are each independently a group consisting of an alkyl group having 1 to 20 carbon atoms, a monocyclic, bicyclic or tricyclic aryl group having 6 to 20 carbon atoms, an oxygen atom, a nitrogen atom, and a sulfur atom. A monocyclic, bicyclic or tricyclic heteroaryl group having 3 to 15 carbon atoms containing 1 to 5 heteroatoms selected from: a monocyclic, bicyclic or tricyclic cyclocarbon having 3 to 15 carbon atoms An alkyl group and a monocyclic, bicyclic or tricyclic heterocycloalkyl group having 3 to 15 carbon atoms and containing 1 to 5 heteroatoms selected from the group consisting of oxygen, nitrogen and sulfur atoms Any one group selected from the group. Two or more groups selected from the group consisting of R1, R2, and R3 may be bonded to form a cyclic structure, and the cyclic structure is selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom. 1 or 2 or more heteroatoms may be present in the ring. However, when X ₁ , X ₂ , and X ₃ are hydrogen atoms or silanol groups, R1, R2, and R3 are not present.

R4, R5, R6, R7, R8, and R9 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a silanol group, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 6 to 20 carbon atoms. A monocyclic, bicyclic or tricyclic ring having 3 to 15 carbon atoms containing 1 to 5 heteroatoms selected from the group consisting of monocyclic, bicyclic or tricyclic aryl groups, oxygen atoms, nitrogen atoms and sulfur atoms 1 to 5 heteroatoms selected from the group consisting of a heteroaryl group of the formula, a monocyclic, bicyclic or tricyclic cycloalkyl group having 3 to 15 carbon atoms, and an oxygen atom, a nitrogen atom and a sulfur atom. It is any one atom or group selected from the group consisting of monocyclic, bicyclic or tricyclic heterocycloalkyl groups having 3 to 15 carbon atoms. R4 and R6 or R6 and R9 may be combined to form an unsaturated bond with the existing carbon-carbon bond.
R10 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a monocyclic, bicyclic or tricyclic aryl group having 6 to 20 carbon atoms, an oxygen atom, a nitrogen atom and a sulfur atom. C3-C15 monocyclic, bicyclic or tricyclic heteroaryl groups containing 5 heteroatoms, C3-C15 monocyclic, bicyclic or tricyclic cycloalkyl groups, and oxygen Selected from the group consisting of monocyclic, bicyclic or tricyclic heterocycloalkyl groups having 3 to 15 carbon atoms and containing 1 to 5 heteroatoms selected from the group consisting of atoms, nitrogen atoms and sulfur atoms Any one atom or group.
B is a base.

  The gist of the present invention is a curable composition containing the episulfide compound curing agent of the present invention and an episulfide compound.

Furthermore, the gist of the present invention is a cured product of an episulfide compound, wherein the episulfide compound is cured by the episulfide compound curing agent of the present invention.
The gist of the present invention is a curing method for curing an episulfide compound with the compound represented by the general formula (1).

  According to the episulfide compound curing agent of the present invention, the base generation efficiency is excellent, and no outgassing occurs when the episulfide compound is cured, so that the episulfide compound can be cured quickly and the cured product can be cured. The effect that bubbles do not remain is obtained. Moreover, the curable composition containing the hardening | curing agent of this invention and an episulfide compound has the effect excellent in storage stability, and can ensure sufficient working time.

  The present invention is described in detail below. In the present invention, the curing agent for an episulfide compound includes not only those acting as a curing agent but also those acting as a curing accelerator (curing aid) as a concept.

[Curing agent for episulfide compounds]
The episulfide compound curing agent of the present invention is characterized by comprising a compound represented by the following general formula (1).

Of the chemical structure represented by the general formula (1), the basic structural sites contributing to the generation of the base (B) are the following structural sites, among which the carboxylate group (—COO—) and the ethylenic double bond (C═CH ₂ ) is a group that directly contributes to the cyclized base generation mechanism.

  That is, the structural site in the general formula (1) is a characteristic site that efficiently cures the episulfide compound by generating a base (B) as an active species by light irradiation (hν) as shown below. It is.

On the other hand, R1 to R10 in the formula (1), and X ₁ to X ₃ is an optional substituent attached to the basic skeleton which is a characteristic portion, or inhibit the base generator mechanism according to the present invention, or cure a subject As long as the substituent is less likely to inhibit curing of the episulfide compound, any substituent may be used. However, those that dare specified below R1 to R10, and _X 1 to X ₃ in the present invention.

In the anion structure portion in the general formula (1), X ₁ , X ₂ , and X ₃ are each independently a hydrogen atom, an oxygen atom, an alkylene group having 1 to 3 carbon atoms, a sulfur atom, a sulfonyl group, and One atom or group selected from the group consisting of silanol groups.
When X ₁ , X ₂ , and X ₃ are not a hydrogen atom or a silanol group, in other words, an oxygen atom, an alkylene group having 1 to 3 carbon atoms, a sulfur atom, or a sulfonyl group, X ₁ , X ₂ , And X ₃ each independently represent an alkyl group having 1 to 20 carbon atoms, a monocyclic, bicyclic or tricyclic aryl group having 6 to 20 carbon atoms, oxygen atom A monocyclic, bicyclic or tricyclic heteroaryl group containing 1 to 5 heteroatoms selected from the group consisting of a nitrogen atom and a sulfur atom, a monocyclic ring having 3 to 15 carbon atoms , A bicyclic or tricyclic cycloalkyl group, and a monocyclic, bicyclic or tricyclic having 3 to 15 carbon atoms containing 1 to 5 heteroatoms selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom Consists of a cyclic heterocycloalkyl group Is any one group selected from. _In the case X 1, _{X 2,} and _{X 3} is a hydrogen atom or a silanol group, R1, R2, and R3 are absent.
Two or more groups selected from the group consisting of R1, R2, and R3 may be bonded to form a cyclic structure, and the cyclic structure is selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom. 1 or 2 or more heteroatoms may be present in the ring.

  In the present invention, an aryl group means a cyclic unsaturated compound, and includes, for example, an unsaturated three-membered ring or a five-membered ring.

R4, R5, R6, R7, R8, and R9 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a silanol group, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 6 to 20 carbon atoms. A monocyclic, bicyclic or tricyclic ring having 3 to 15 carbon atoms containing 1 to 5 heteroatoms selected from the group consisting of monocyclic, bicyclic or tricyclic aryl groups, oxygen atoms, nitrogen atoms and sulfur atoms 1 to 5 heteroatoms selected from the group consisting of a heteroaryl group of the formula, a monocyclic, bicyclic or tricyclic cycloalkyl group having 3 to 15 carbon atoms, and an oxygen atom, a nitrogen atom and a sulfur atom. It is any one atom or group selected from the group consisting of monocyclic, bicyclic or tricyclic heterocycloalkyl groups having 3 to 15 carbon atoms. R4 and R6 or R6 and R9 may be combined to form an unsaturated bond with the existing carbon-carbon bond.

R10 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a monocyclic, bicyclic or tricyclic aryl group having 6 to 20 carbon atoms, an oxygen atom, a nitrogen atom and a sulfur atom. C3-C15 monocyclic, bicyclic or tricyclic heteroaryl group containing 5 heteroatoms, C3-C15 monocyclic, bicyclic or tricyclic cycloalkyl group, and oxygen atom Any one selected from the group consisting of a monocyclic, bicyclic or tricyclic heterocycloalkyl group having 3 to 15 carbon atoms containing 1 to 5 heteroatoms selected from the group consisting of nitrogen and sulfur atoms Or a single atom or group.

  Examples of the alkyl group having 1 to 20 carbon atoms include linear or branched alkyl groups such as a methyl group, an ethyl group, a propyl group, and an isopropyl group. The carbon number is preferably 1 to 18, and more preferably 1 to 15 preferable.

Examples of the monocyclic, bicyclic or tricyclic aryl group having 6 to 20 carbon atoms include phenyl group, benzyl group, tolyl group, naphthyl group, phenanthryl group, anthracenyl group and the like, and preferably 6 to 18 carbon atoms. 6 to 15 are more preferable.

  Examples of the monocyclic, bicyclic or tricyclic heteroaryl group having 3 to 15 carbon atoms containing 1 to 5 heteroatoms selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom include furanyl, benzofuranyl, Examples include thienyl, thioxanthenyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, pyrazinyl, pyrimidinyl, indolizinyl, isoindolyl, purinyl, naphthyridinyl, carbazolyl, and the number of carbon atoms is preferably 3-14, more preferably 3-13. The number of heteroatoms is preferably 1 to 4, and may contain heterogeneous heteroatoms.

  Examples of the monocyclic, bicyclic, or tricyclic cycloalkyl group having 3 to 15 carbon atoms include cyclopropane, cyclohexane, and cycloheptane. The number of carbon atoms is preferably 3 to 14, and more preferably 3 to 13.

  As monocyclic, bicyclic or tricyclic heterocycloalkyl groups having 3 to 15 carbon atoms and containing 1 to 5 heteroatoms selected from the group consisting of oxygen atom, nitrogen atom and sulfur atom, tetrahydrofuranyl, Tetrahydropyranyl, tetrahydrothienyl, 1-methylpyrrolidinyl and the like can be mentioned, and the number of carbon atoms is preferably 3-14, more preferably 3-13. The number of heteroatoms is preferably 1 to 4, and may contain heterogeneous heteroatoms.

  Examples of the halogen atom include an iodine atom, a bromine atom, a chlorine atom, and a fluorine atom.

In the cation structure portion in the general formula (1), B is a base, and examples thereof include the following amine compounds.
Aliphatic first such as methylamine, ethylamine, propylamine, hexylamine, octylamine, decylamine, dodecylamine, hexadecylamine, octadecylamine, ethylenediamine, 1,3-propanediamine, 1,6-hexanediamine, diethylenetriamine, etc. Secondary amine compounds;
Cycloaliphatic primary amine compounds such as cyclohexylamine, 1,3- (bisaminoethyl) cyclohexane, diaminocyclohexane, isophoronediamine;
Aromatic primary amine compounds such as benzylamine, aniline, metaphenylenediamine, metaxylenediamine;
Aliphatic secondary amine compounds such as dimethylamine, diethylamine, dibutylamine, dihexylamine, dioctylamine, didecylamine, ethylmethylamine;
Alicyclic secondary amine compounds such as aziridine, azetidine, pyrrolidine, piperidine, norbornane dimethylamine, 1,3-bis (4-piperidyl) propane;
Aromatic secondary amine compounds such as benzylmethylamine, diphenylamine, dibenzylamine;
Triethylamine, tributylamine, trihexylamine, trioctylamine, tridecylamine, ethyldiisopropylamine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), 1,5 Aliphatic tertiary amine compounds such as 7-triazabicyclo [4.4.0] dec-5-ene (TBD), 1,4-diazabicyclo [2.2.0] octane, phosphazene base;
Pyridine compounds such as pyridine, 2,4,6-trimethylpyridine, 2,6-di (t-butyl) pyridine, imidazole, 2-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, 2-ethyl- Examples include imidazole compounds such as 4-methylimidazole and 1-benzyl-2-methylimidazole, and aromatic tertiary amine compounds such as triphenylamine, methyldiphenylamine, diethylaniline, and tribenzylamine.
Among these, an aliphatic tertiary amine compound or an aromatic tertiary amine compound is preferable in that it can be used in a small amount when used as a curing agent. Among them, 1,8-diazabicyclo [5.4.0] is preferable. ] -7-undecene (DBU), 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD), phosphazene base, imidazole, 2-methylimidazole and the like are preferable.

  In the general formula (1), a compound in which R4, R5, R6, R7, R8 and R9 are all hydrogen atoms and R10 is a methyl group, that is, a compound represented by the following general formula (2) is preferable.

X ₁ , X ₂ , X ₃ , R ₁ , R 2 and R _{3 in} the general formula (2) are the same as those in the general formula (1).

Among the compounds represented by the general formula (2), in the anion structure portion, X ₁ is an oxygen atom, X ₂ and X ₃ are all hydrogen atoms, R 1 is an alkyl group having 1 to 20 carbon atoms, , X ₁ and X ₂ are all hydrogen atoms, X ₃ is an oxygen atom, and R ₃ is preferably an alkyl group having 1 to 20 carbon atoms, and X ₁ is an oxygen atom, X ₂ and X ₃ are all those hydrogen atom, R1 is a methyl group, also, X _1, and X ₂ are both hydrogen atoms, X ₃ is an oxygen atom, R3 is is more preferable a methyl group.
As for the cation partial structure, the base B is 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), 1,5,7-triazabicyclo [4.4.0] dec-5. -Ene (TBD), phosphazene base, imidazole, 2-methylimidazole and the like are preferable.

  The compound represented by the general formula (1) can be produced by a known method. For example, it can be produced by the method described in JP2012-250969A.

  The episulfide compound targeted by the curing agent for episulfide compound of the present invention is a monofunctional episulfide compound or one having one or more episulfide groups in one molecule, and various known epoxy resins, thiocyanates, thio It can be easily obtained by reacting a sulfurizing agent such as urea in the presence of a suitable solvent and replacing the oxygen atom of the epoxy group with a sulfur atom. When the oxygen atom of the epoxy group is substituted with a sulfur atom, the oxygen atom of all the epoxy groups may be substituted with a sulfur atom, or some of the oxygen atoms of the epoxy group are substituted with sulfur atoms. It may be.

Especially, the following are illustrated as a typical episulfide compound.
(1) Bisphenol type obtained by glycidylating bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, etc. A bisphenol-type episulfide resin obtained by further thioglycidylating an epoxy resin;
(2) Glycidyl is a nuclear hydrogenated product of bisphenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, tetrabromobisphenol A, etc. A hydrogenated bisphenol-type episulfide resin obtained by further thioglycidylating a hydrogenated bisphenol-type epoxy resin obtained by the conversion;
(3) An episulfide resin obtained by further thioglycidating an epoxy resin obtained by glycidylating other dihydric phenols such as biphenol, dihydroxynaphthalene, dihydroxyanthracene, and 9,9-bis (4-hydroxyphenyl) fluorene;
(4) 1,1,1-tris (4-hydroxyphenyl) methane, 4,4- (1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol, etc. An episulfide resin obtained by further thioglycidylating an epoxy resin obtained by glycidylating trisphenols;
(5) An episulfide resin obtained by further thioglycidylating an epoxy resin obtained by glycidylating tetrakisphenols such as 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane;
(6) A novolac-type episulfide resin obtained by further thioglycidating a novolac-type epoxy resin obtained by glycidylating phenol novolak, cresol novolak, bisphenol A novolak, brominated phenol novolak, brominated bisphenol A novolak, etc .;
(7) An aliphatic ether type episulfide resin obtained by further thioglycidylating an aliphatic ether type epoxy resin obtained by glycidylating a polyhydric alcohol such as glycerin or polyethylene glycol;
(8) An ether ester type episulfide resin obtained by further thioglycidylating an ether ester type epoxy resin obtained by glycidylating a hydroxycarboxylic acid such as p-oxybenzoic acid or β-oxynaphthoic acid;
(9) An ester-type episulfide resin obtained by further thioglycidylating an ester-type epoxy resin obtained by glycidylating a polycarboxylic acid such as phthalic acid or terephthalic acid;
(10) An amine type episulfide resin obtained by further thioglycidylating an amine type epoxy resin or triglycidyl isocyanurate obtained by glycidylating an amine compound such as 4,4-diaminodiphenylmethane or m-aminophenol;
(11) A thioglycidylation product of a polyamide polyamine of a polyalkylene polyamine such as diethylenetriamine or triethylenetetramine and a dicarboxylic acid such as adipic acid;
(12) Fats such as 3,4-epithiocyclohexylmethyl-3 ′, 4′-epithiocyclohexanecarboxylate, bis- (3,4-epithiocyclohexyl) adipate, 1,2-epithio-4-vinylcyclohexane Cyclic episulfide;
(13) A silicone-modified episulfide resin obtained by a reaction of an organopolysiloxane with an episulfide resin or a phenol novolac type episulfide resin;
(14) Episulfide compounds such as thioglycidyl methacrylate, 3,4-epithiocyclohexylmethyl methacrylate, propylene sulfide, cyclohexane sulfide, and polymers thereof;
(15) Episulfide compounds such as bis (2,3-epithiopropyl) sulfide, bis (2,3-epithiopropylthio) ethane, and bis (5,6-epithio-3-thiohexane) sulfide;
Etc. One episulfide compound selected from these episulfide compounds or a mixture of two or more episulfide compounds can be used.

  Moreover, these episulfide compounds are suitably selected according to the use of hardened | cured material. For example, (2), (10), (11), and (12) episulfide compounds are used for polarizing plate adhesives, and (2), (10), (12), (14), (15) are used for semiconductor resists. ) Episulfide compounds, organic EL device encapsulants, (3) and (13) episulfide compounds, and LED encapsulants, (2), (10), (12), (13) episulfide compounds, prints In the insulating material for wiring boards, the episulfide compounds (1), (3), and (6) are preferably used.

The episulfide compound preferably has an episulfide equivalent (average molecular weight per episulfide group) of 50 to 2,000, and more preferably 50 to 1,800. If the episulfide equivalent is too small, it tends to be difficult to control the reaction during curing. On the other hand, if the episulfide equivalent is too large, the compatibility with the curing agent for episulfide compounds and the solvent tends to decrease.
The episulfide equivalent of the episulfide compound can be calculated from gel permeation chromatography and the number of episulfide functional groups of the compound.

(Curable composition)
The curable composition of this invention contains the hardening | curing agent for episulfide compounds of this invention, and said episulfide compound, It is characterized by the above-mentioned.

  The content of the curing agent for the episulfide compound in the curable composition of the present invention is preferably 0.1 to 60 parts by weight, and 0.5 to 50 parts by weight with respect to 100 parts by weight of the episulfide compound. Is more preferable, and it is still more preferable to set it as 1-40 weight part. When there is too little content of a hardening | curing agent, there exists a tendency for it to become difficult to make an episulfide compound react rapidly. On the other hand, when the content is too large, the curing agent itself tends to reduce the solubility of the episulfide compound, and tends to be disadvantageous in cost.

  In the curable composition of the present invention, if necessary, a base proliferating agent that generates a base proliferatively by the action of a base is usually 1 to 40 parts by weight, preferably 100 parts by weight of the episulfide compound. 5 to 20 parts by weight can be contained. Moreover, a sensitizer can be contained normally 1-30 weight part with respect to 100 weight part of episulfide compounds, Preferably it is 2-20 weight part.

Moreover, the curable composition of this invention can be made to contain a solvent as needed. Examples of such solvents include aromatic hydrocarbon compounds such as toluene; saturated or unsaturated hydrocarbon compounds such as hexane and heptane; ethers such as diethyl ether and tetrahydrofuran; ketones such as acetone and methyl ethyl ketone; Examples thereof include esters, alcohols such as ethanol and isopropyl alcohol, and halogen solvents such as chloroform. One type of solvent selected from these solvents or a mixed solvent obtained by mixing two or more types can be used.
In the curable composition of the present invention, the solvent content is applied uniformly when, for example, the curable composition is applied on a predetermined substrate and a layer is formed of the curable composition. Can be appropriately selected.

  In addition, the curing agent for episulfide compounds of the present invention (hereinafter also referred to as the curing agent of the present invention) can be used as a curing accelerator that accelerates curing by the curing agent. For example, the following known curing agents are used.

  Acid anhydrides: aromatic anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride , Cycloaliphatic acid anhydrides such as methylendomethylenetetrahydrophthalic anhydride, dodecenyl succinic anhydride, trialkyltetrahydrophthalic anhydride, and the like in which these oxygen atoms are substituted with sulfur atoms.

  Polyhydric phenols: catechol, resorcin, hydroquinone, bisphenol F, bisphenol A, bisphenol S, biphenol, phenol novolacs, cresol novolacs, bisphenol A and other dihydric phenol novolacs, trishydroxyphenylmethanes, aralkyl polyphenols , Dicyclopentadiene polyphenols, and the like, and those oxygen atoms substituted with sulfur atoms.

These curing agents may be used alone or in combination of two or more. The use ratio of the curing agent described above is usually 0.01 to 200 parts by weight, preferably 10 to 100 parts by weight, with respect to 100 parts by weight of the episulfide compound.
Moreover, content of the hardening | curing agent of this invention as a hardening accelerator is 0.01-10 weight part normally with respect to 100 weight part of episulfide compounds, Preferably it is 0.1-5 weight part.
Furthermore, with respect to 100 parts by weight of the known curing agent, the curing agent of the present invention as a curing accelerator is preferably 0.1 to 10 parts by weight, and more preferably 1 to 5 parts by weight. It is preferable.

  The curable composition of the present invention may further contain various additives as long as the objects and effects of the present invention are not hindered. Examples of such additives include fillers, pigments, dyes, leveling agents, antifoaming agents, antistatic agents, ultraviolet absorbers, pH adjusting agents, dispersants, dispersion aids, surface modifiers, plasticizers, plasticizers. Examples include accelerators, sagging inhibitors, curing accelerators, and photoacid generators. 1 type (s) or 2 or more types selected from these additives can be used.

  The curable composition of the present invention may further contain various curable monomers, oligomers or synthetic resins for the purpose of improving the properties of the cured product in the final coating film, adhesive layer, molded article, and the like. it can. For example, diluent for epoxy resin such as monoepoxy, general aromatic and alicyclic epoxy resin, phenol resin, alkyd resin, melamine resin, fluororesin, vinyl chloride resin, acrylic resin, silicone resin, polyester resin, etc. One type or a combination of two or more types can be mentioned. These blending ratios may be in an amount that does not impair the original properties of the curable composition of the present invention, and are usually 100 parts by weight or less, particularly 50 parts by weight or less with respect to 100 parts by weight of the episulfide compound. Is preferred.

  The curable composition of this invention is manufactured by physically mixing the hardening | curing agent for episulfide compounds of this invention, an episulfide compound, and arbitrary components by a well-known means and conditions. As a method of mixing the episulfide compound curing agent and the episulfide compound of the present invention, for example, a predetermined amount of the curing agent, the episulfide compound, and an optional component are kneaded using a roll kneader, a kneader, an extruder, or the like. A method is mentioned.

[Curing method of episulfide compound]
In the present invention, the episulfide compound can be cured by the compound represented by the general formula (1). For example, the curable composition containing the episulfide compound curing agent of the present invention and the episulfide compound can be cured by light irradiation or heating.
By the action of light or heat, a base is generated in the curable composition of the present invention, the episulfide compound is cured by polymerization, and a cured product of the episulfide compound is formed.

In the case where the curable composition of the present invention is cured by ultraviolet irradiation, generally integrated irradiation dose 10~10,000mJ / cm ^2, preferably be cured by irradiation of ultraviolet light of 10~8000mJ / cm ² it can. The output wavelength is preferably ultraviolet light having a light emission distribution at a wavelength of 400 nm or less.

  The ultraviolet ray source used for the ultraviolet ray irradiation is not particularly limited as long as it can output a wavelength in the vicinity of 256 to 365 nm. For example, various known types such as a high pressure mercury lamp, a metal halide lamp, a high power metal halide lamp, a xenon lamp, and an LED. Can be used. Among these, a high pressure mercury lamp and a metal halide lamp are preferably used.

  Since the curing reaction by ultraviolet irradiation is easily inhibited by oxygen, the atmosphere at the time of ultraviolet irradiation is preferably 3% or less, more preferably 0.5% or less, and particularly preferably 0.3% or less.

  The curable composition of the present invention undergoes a polymerization reaction even at room temperature after ultraviolet irradiation, but is preferably heat-treated in order to cure efficiently. The conditions for the heat treatment may be appropriately determined according to various conditions such as illuminance, integrated dose, type of base generated from the photobase generator used, type of base curable compound, etc. It is 30-200 degreeC, It is preferable to set it as 40-150 degreeC, and it is especially preferable that it is 50-130 degreeC. The heating time is usually 10 seconds to 1 day, preferably 60 seconds to 360 minutes, and particularly preferably 5 minutes to 120 minutes.

  Since the curable composition of the present invention contains the episulfide compound curing agent of the present invention and the episulfide compound, the reaction between the base generated from the curing agent and the episulfide compound proceeds in a chain manner with high generation efficiency, Curing speed and reaction efficiency are excellent, and curing is performed quickly. Further, since no outgas is generated when the episulfide compound is cured, an effect that no bubbles remain in the cured product can be obtained. The curable composition of the present invention exhibiting such effects can be suitably used for, for example, a highly sensitive photocuring material, resist material (pattern forming material), and the like. Moreover, the curable composition of this invention is excellent in storage stability.

  A cured product of an episulfide compound cured by the episulfide compound curing agent of the present invention is widely used as a member in a field in which properties such as heat resistance, dimensional stability, and insulation properties are effective. Printing ink, organic EL and LED sealing sealant and adhesive, polarizing plate adhesive, color filter, organic EL light extraction layer and light extraction film, display substrate, flexible display substrate, flexible display film, semiconductor Widely used as a component of equipment, electronic parts, interlayer insulation films, wiring coating films, optical circuits, optical circuit parts, antireflection films, holograms, optical members or building materials. Color filters, display substrates, flexible display substrates, flexible display substrates Lum, semiconductor device, electronic component, an interlayer insulating film, the wiring covering film, an optical circuit, an optical circuit component, the anti-reflection film, holographic, optical element or building components and the like is provided. Moreover, the pattern etc. formed as hardened | cured material are equipped with heat resistance and insulation, for example, transparent sealing agent, a color filter, a display substrate, a flexible display substrate, a film for flexible displays, an electronic component, a semiconductor device, interlayer insulation It can be advantageously used as a film, a wiring coating film, an optical circuit, an optical circuit component, an antireflection film, other optical members or electronic members.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to a following example, unless the summary is exceeded. In the examples, “%” and “parts” mean weight basis.

[Synthesis Example 1]
“Synthesis of 8-bromo-7-methoxy-3,4-dihydro-2H-naphthalen-1-one (i)”
To a 500 ml reactor, 20.00 g (0.11 mol) of 7-methoxy-3,4-dihydro-2H-naphthalen-1-one, 23.14 g (0.13 mol) of N-bromosuccinimide and 200 ml of acetonitrile were added. The entire reactor was shielded from light and reacted at room temperature for 30 hours. After completion of the reaction, the reaction solution was washed with 300 ml of water three times and then concentrated to obtain a crude product.
The resulting crude product was purified by silica gel column chromatography (ethyl acetate / hexane = 1/7 (volume ratio)) to give 8-bromo-7-methoxy-3,4-dihydro-2H-naphthalene-1. -23.28g of on (i) was obtained. The yield was 83%.

[Synthesis Example 2]
“Synthesis of 8-bromo-1-ethylidene-7-methoxy-1,2,3,4-tetrahydronaphthalene (ii)”
Under a nitrogen atmosphere, 37.28 g (0.10 mol) of ethyltriphenylphosphonium bromide, 8.64 g (0.08 mol) of potassium t-butoxy and 90 ml of tetrahydrofuran were added to a 500 ml reactor, and the mixture was stirred at room temperature for 1 hour. Next, a 40 ml tetrahydrofuran solution of 20.15 g (0.08 mol) of 8-bromo-7-methoxy-3,4-dihydro-2H-naphthalen-1-one (i) obtained in Synthesis Example 1 was used as a reaction mixture. The solution was added dropwise, and reacted at room temperature for 16 hours after the completion of the addition. After completion of the reaction, dilute hydrochloric acid was added to the reaction solution, and the mixture was washed 3 times with 200 ml of dichloromethane. The obtained organic layer was concentrated, 700 ml of hexane was added to the concentrated solution, and the mixture was stirred for 30 minutes. Next, the precipitated crystals were removed by filtration, and the obtained filtrate was concentrated to obtain a crude product.
The resulting crude product was purified by silica gel column chromatography (ethyl acetate / hexane = 1/5 (volume ratio)) to give 8-bromo-1-ethylidene-7-methoxy-1,2,3,4. -16.36 g of tetrahydronaphthalene (ii) was obtained. The yield was 79%.

[Synthesis Example 3]
“Synthesis of 8-ethylidene-2-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid (iii)”
Under a nitrogen atmosphere, 1.46 g (0.06 mol) of magnesium and 80 ml of tetrahydrofuran were added to a 500 ml reactor and stirred at room temperature for 10 minutes. Next, a 40 ml tetrahydrofuran solution containing 8.55 g (0.03 mol) of 8-bromo-1-ethylidene-7-methoxy-1,2,3,4-tetrahydronaphthalene (ii) obtained in Synthesis Example 2 was added to the reaction mixture. And then refluxed with heating for 1 hour. After completion of heating and refluxing, the reaction solution was poured into a large excess of dry ice (approximately 500 g) and allowed to stand until the dry ice sublimated. Thereafter, dilute hydrochloric acid was added to the reaction solution, and the mixture was washed 3 times with 200 ml of dichloromethane. The obtained organic layer was concentrated to obtain a crude product.
The obtained crude product was purified by silica gel column chromatography (ethyl acetate / hexane = 1/5 (volume ratio)) to give 8-ethylidene-2-methoxy-5,6,7,8-tetrahydronaphthalene-1. -4.53g of carboxylic acid (iii) was acquired. The yield was 61%.

[Production Example 1]
"Synthesis of 8-ethylidene-2-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid diazabicycloundecene"
In a 500 ml reactor, 1.00 g (4.3 mmol) of 8-ethylidene-2-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid (iii) obtained in Synthesis Example 3 was added. -0.66 g (4.3 mmol) of diazabicyclo [5.4.0] -7-undecene and 250 ml of diethyl ether were added and reacted at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain 1.38 g of 8-ethylidene-2-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid diazabicycloundecene salt shown below. I got it. The yield was 83%.

[Production Example 2]
“Synthesis of 8-ethylidene-2-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid triazabicyclodecaene salt”
Into a 200 ml reactor, 1.00 g (4.3 mmol) of 8-ethylidene-2-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid (iii) obtained in Synthesis Example 3, 1,5 , 7-triazabicyclo [4.4.0] dec-5-ene (0.60 g, 4.3 mmol) and 100 ml of diethyl ether were added and reacted at room temperature for 1 hour. After completion of the reaction, the precipitated crystals were collected by filtration, and 1-ethyltriazabicyclodecaene salt of 8-ethylidene-2-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid shown below was 1 .47 g was obtained. The yield was 92%.

[Production Example 3]
“Synthesis of 8-ethylidene-2-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid phosphazene base salt”
In a 200 ml reactor, 0.80 g (3.4 mmol) of 8-ethylidene-2-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid (iii) obtained in Synthesis Example 3 and phosphazene base 0 .61 g (3.4 mmol) and 100 ml of diethyl ether were added and reacted at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain 1.41 g of 8-ethylidene-2-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid phosphazene base salt shown below. The yield was 100%.

[Production Example 4]
“Synthesis of 8-ethylidene-2-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid imidazole salt”
In a 1 L reactor, 1.96 g (8.4 mmol) of 8-ethylidene-2-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid (iii) obtained in Synthesis Example 3 and imidazole 0. 57 g (8.4 mmol) and 500 ml of diethyl ether were added and reacted at room temperature for 1 hour. After completion of the reaction, the precipitated crystals were collected by filtration to obtain 1.72 g of 8-ethylidene-2-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid imidazole salt shown below. . The yield was 68%.

[Synthesis Example 4]
"Synthesis of 8-bromo-5-methoxy-3,4-dihydro-2H-naphthalen-1-one (iv)"
To a 500 ml reactor were added 20.00 g (0.11 mol) of 5-methoxy-3,4-dihydro-2H-naphthalen-1-one, 23.14 g (0.13 mol) of N-bromosuccinimide and 200 ml of acetonitrile. The entire reactor was shielded from light and reacted at room temperature for 48 hours. After completion of the reaction, the reaction solution was washed with 300 ml of water three times and then concentrated to obtain a crude product.
The resulting crude product was purified by silica gel column chromatography (ethyl acetate / hexane = 1/7 (volume ratio)) to give 8-bromo-5-methoxy-3,4-dihydro-2H-naphthalene-1. -25.98g of on (iv) was obtained. The yield was 89%.

[Synthesis Example 5]
“Synthesis of 8-bromo-1-ethylidene-5-methoxy-1,2,3,4-tetrahydronaphthalene (v)”
Under a nitrogen atmosphere, 37.28 g (0.10 mol) of ethyltriphenylphosphonium bromide, 8.64 g (0.08 mol) of potassium t-butoxy and 90 ml of tetrahydrofuran were added to a 500 ml reactor, and the mixture was stirred at room temperature for 1 hour. Next, a 40 ml tetrahydrofuran solution of 20.15 g (0.08 mol) of 8-bromo-5-methoxy-3,4-dihydro-2H-naphthalen-1-one (iv) obtained in Synthesis Example 4 was used as a reaction mixture. The solution was added dropwise, and reacted at room temperature for 16 hours after the completion of the addition. After completion of the reaction, dilute hydrochloric acid was added to the reaction solution, and the mixture was washed 3 times with 200 ml of dichloromethane. The obtained organic layer was concentrated, 700 ml of hexane was added to the concentrated solution, and the mixture was stirred for 30 minutes. Next, the precipitated crystals were removed by filtration, and the obtained filtrate was concentrated to obtain a crude product.
The resulting crude product was purified by silica gel column chromatography (ethyl acetate / hexane = 1/5 (volume ratio)) to give 8-bromo-1-ethylidene-5-methoxy-1,2,3,4. -13.78 g of tetrahydronaphthalene (v) was obtained. The yield was 65%.

[Synthesis Example 6]
“Synthesis of 8-ethylidene-4-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid (vi)”
Under a nitrogen atmosphere, 1.46 g (0.06 mol) of magnesium and 80 ml of tetrahydrofuran were added to a 500 ml reactor and stirred at room temperature for 10 minutes. Next, a 40 ml tetrahydrofuran solution containing 8.55 g (0.03 mol) of 8-bromo-1-ethylidene-5-methoxy-1,2,3,4-tetrahydronaphthalene (v) obtained in Synthesis Example 5 was added to the reaction mixture. And then refluxed with heating for 1 hour. After completion of heating and refluxing, the reaction solution was poured into a large excess of dry ice (approximately 500 g) and allowed to stand until the dry ice sublimated. Thereafter, dilute hydrochloric acid was added to the reaction solution, and the mixture was washed 3 times with 200 ml of dichloromethane. The obtained organic layer was concentrated to obtain a crude product.
The obtained crude product was purified by silica gel column chromatography (ethyl acetate / hexane = 1/5 (volume ratio)) to give 8-ethylidene-4-methoxy-5,6,7,8-tetrahydronaphthalene-1. -4.00 g of carboxylic acid (vi) was obtained. The yield was 54%.

[Production Example 5]
"Synthesis of 8-ethylidene-4-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid diazabicycloundecene"
In a 500 ml reactor, 1.00 g (4.3 mmol) of 8-ethylidene-4-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid (vi) obtained in Synthesis Example 6 was added. -0.66 g (4.3 mmol) of diazabicyclo [5.4.0] -7-undecene and 250 ml of diethyl ether were added and reacted at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain 1.67 g of 8-ethylidene-4-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid diazabicycloundecene salt shown below. I got it. The yield was 100%.

[Production Example 6]
“Synthesis of 8-ethylidene-4-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid triazabicyclodecaene salt”
In a 200 ml reactor, 0.31 g (1.3 mmol) of 8-ethylidene-4-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid (vi) obtained in Synthesis Example 6 and 1,5 , 7-triazabicyclo [4.4.0] dec-5-ene (0.19 g, 1.3 mmol) and diethyl ether (120 ml) were added and reacted at room temperature for 1 hour. After completion of the reaction, the precipitated crystals were collected by filtration, and the following 8-ethylidene-4-methoxy-5,6,7, -tetrahydronaphthalene-1-carboxylic acid triazabicyclodecaene salt was reduced to 0.0. 34 g was obtained. The yield was 69%.

[Production Example 7]
“Synthesis of 8-ethylidene-4-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid phosphazene base salt”
In a 200 ml reactor, 0.23 g (1.0 mmol) of 8-ethylidene-4-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid (vi) obtained in Synthesis Example 6 and phosphazene base 0 were added. .18 g (1.0 mmol) and diethyl ether 50 ml were added and reacted at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain 0.40 g of 8-ethylidene-4-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid triazabicyclodecaene salt shown below. I got it. The yield was 97%.

[Comparative Production Example 1]
“Synthesis of 2- (3-benzoylphenyl) propionic acid diazabicycloundecene salt”
In a 100 ml reactor, 3.0 g (11.8 mmol) 2- (3-benzoylphenyl) propionic acid, 1.80 g (11.8 mmol) 1,8-diazabicyclo [5.4.0] -7-undecene, diethyl 30 ml of ether was added and reacted at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain 4.96 g of 2- (3-benzoylphenyl) propionic acid diazabicycloundecene salt shown below. The yield was 100%.

[Comparative Production Example 2]
“Synthesis of 2- (3-benzoylphenyl) propionic acid triazabicyclodecaene salt”
In a 100 ml reactor, 1.00 g (3.9 mmol) of 2- (3-benzoylphenyl) propionic acid, 0.55 g of 1,5,7-triazabicyclo [4.4.0] dec-5-ene (3 0.9 mmol) and 150 ml of diethyl ether were added and reacted at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain 1.73 g of 2- (3-benzoylphenyl) propionic acid triazabicyclodecaene salt shown below. The yield was 100%.

[Examples 1-7, Comparative Examples 1-2]
The compounds produced in Production Examples 1-7 were used as curing agents in Examples 1-7, the compounds produced in Comparative Production Examples 1-2 were used as curing agents in Comparative Examples 1-2, and the following evaluation was performed. It was.

〔Evaluation item〕
(1) Insolubilization rate measurement (base generation efficiency)
A homogeneous solution was prepared by mixing 8 parts of a curing agent and 100 parts of chloroform with respect to 100 parts of a nuclear hydrogenated bisphenol A type episulfide resin (manufactured by Mitsubishi Chemical Corporation, YL-7007). This prepared liquid was coated on an alkali-free glass using a bar coater (No. 20), and prebaked at 50 ° C. for 5 minutes. Using a metal halide lamp, after irradiating ultraviolet rays with an exposure amount of 928 mJ / cm ^{2 in} terms of 365 nm, heat treatment was performed at the temperature shown in Table 1 for 40 minutes to obtain a cured film. The obtained cured film was immersed in chloroform for 30 seconds, then taken out from chloroform and dried. The insolubilization rate was determined from the difference in weight of the cured film before and after immersion in chloroform. The results are shown in Table 1.

(2) Confirmation of bubble generation 8 parts of curing agent was mixed with 100 parts of nuclear hydrogenated bisphenol A type episulfide resin (Mitsubishi Chemical Corporation, YL-7007). A sample was prepared by defoaming the mixed liquid using a defoamer. The prepared sample is put into a mold made of a silicon spacer having a thickness of 2 mm, and sandwiched between two non-alkali glasses through a release film. Using a metal halide lamp, an ultraviolet ray with an exposure amount of 2145 mJ / cm ² is converted to 365 nm. Irradiated. Subsequently, after heat-processing for 1 hour at the temperature of Table 1, it removed from the mold and obtained about 2 mm plate-shaped hardened | cured material. About the obtained hardened | cured material, it confirmed visually about the presence or absence of a bubble. The results are shown in Table 1.

[Comparative Example 3]
In Example 6, evaluation was similarly made except that the nuclear hydrogenated bisphenol A type episulfide resin was changed to a bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER828), but a cured film could not be obtained. .

[Comparative Example 4]
In Example 6, evaluation was similarly made except that the nuclear hydrogenated bisphenol A type episulfide resin was changed to a nuclear hydrogenated bisphenol A type epoxy resin (Mitsubishi Chemical Corporation, YX8000), but a cured film could be obtained. could not.

  From the results shown in Table 1, according to the curing agent for episulfide compounds of the present invention, the base generation efficiency is equivalent to the conventional curing agents shown in Comparative Examples 1 and 2, and the episulfide compound can be cured quickly. I understand. Moreover, in the curing agent for episulfide compounds of the present invention, unlike the conventional curing agents shown in Comparative Examples 1 and 2, no outgassing occurs when the episulfide compound is cured, so that no bubbles remain in the cured film. It can also be seen that the effect is obtained. Furthermore, the results of Comparative Examples 3 and 4 indicate that the curing agent of the present invention is particularly excellent in curability for episulfide compounds.

Moreover, the storage stability test was done as follows.
[Storage stability test]
The curable compositions shown in Examples 8 and 9 and Comparative Examples 5 and 6 below were respectively prepared, and the viscosity was twice the initial viscosity using a B-type viscometer (BROOKFIELD, DV-II + Pro) at 25 ° C. The time to reach was measured and the time was evaluated as storage stability.

Example 8
8 parts of the curing agent of Production Example 5 and 16 parts of chloroform were mixed with 100 parts of the nuclear hydrogenated bisphenol A type episulfide resin to prepare a curable composition. The time until the viscosity of the curable composition became twice the initial viscosity at 25 ° C. was measured to evaluate the storage stability. The results are shown in Table 2.

Example 9
8 parts of the curing agent of Production Example 6 and 16 parts of chloroform were mixed with 100 parts of the nuclear hydrogenated bisphenol A type episulfide resin to prepare a curable composition. The time until the viscosity of the curable composition became twice the initial viscosity at 25 ° C. was measured to evaluate the storage stability. The results are shown in Table 2.

[Comparative Example 5]
A curable composition was prepared by mixing 3 parts of 1,8-diazabicyclo [5.4.0] -7-undecene and 16 parts of chloroform with respect to 100 parts of the nuclear hydrogenated bisphenol A type episulfide resin. The time until the viscosity of the curable composition became twice the initial viscosity at 25 ° C. was measured to evaluate the storage stability. The results are shown in Table 2.

[Comparative Example 6]
3 parts of 1,5,7-triazabicyclo [4.4.0] dec-5-ene and 16 parts of chloroform are mixed with 100 parts of nuclear hydrogenated bisphenol A type episulfide resin to obtain a curable composition. Was prepared. The time until the viscosity of the curable composition became twice the initial viscosity at 25 ° C. was measured to evaluate the storage stability. The results are shown in Table 2.

  From the results shown in Table 2, the storage stability of the curable composition using the episulfide compound curing agent of the present invention is determined when a basic compound generally used as a conventional curing agent is used as the curing agent. It turns out that it is far superior.

  The episulfide compound curing agent of the present invention is particularly useful as a curing agent in the field of electronic materials because it has excellent base generation efficiency, does not generate outgas, and has excellent storage stability when used as a curable composition. is there. Further, the episulfide compound cured by the episulfide compound curing agent of the present invention is useful as a member in a field requiring characteristics such as heat resistance, dimensional stability, and insulation, for example, an optical member and an electronic member. is there.

Claims (6)

A curing agent for an episulfide compound, comprising a compound represented by the following general formula (1).

In general formula (1),
X ₁ , X ₂ , and X ₃ are each independently any one selected from the group consisting of a hydrogen atom, an oxygen atom, an alkylene group having 1 to 3 carbon atoms, a sulfur atom, a sulfonyl group, and a silanol group. An atom or group.
R1, R2, and R3 are each independently a group consisting of an alkyl group having 1 to 20 carbon atoms, a monocyclic, bicyclic or tricyclic aryl group having 6 to 20 carbon atoms, an oxygen atom, a nitrogen atom, and a sulfur atom. A monocyclic, bicyclic or tricyclic heteroaryl group having 3 to 15 carbon atoms containing 1 to 5 heteroatoms selected from: a monocyclic, bicyclic or tricyclic cyclocarbon having 3 to 15 carbon atoms An alkyl group and a monocyclic, bicyclic or tricyclic heterocycloalkyl group having 3 to 15 carbon atoms and containing 1 to 5 heteroatoms selected from the group consisting of oxygen, nitrogen and sulfur atoms Any one group selected from the group. Two or more groups selected from the group consisting of R1, R2, and R3 may be bonded to form a cyclic structure, and the cyclic structure is selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom. 1 or 2 or more heteroatoms may be present in the ring. However, when X ₁ , X ₂ and X ₃ are hydrogen atoms or silanol groups, R 1, R 2 and R 3 are not present.
R4, R5, R6, R7, R8, and R9 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a silanol group, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 6 to 20 carbon atoms. A monocyclic, bicyclic or tricyclic ring having 3 to 15 carbon atoms containing 1 to 5 heteroatoms selected from the group consisting of monocyclic, bicyclic or tricyclic aryl groups, oxygen atoms, nitrogen atoms and sulfur atoms 1 to 5 heteroatoms selected from the group consisting of a heteroaryl group of the formula, a monocyclic, bicyclic or tricyclic cycloalkyl group having 3 to 15 carbon atoms, and an oxygen atom, a nitrogen atom and a sulfur atom. It is any one atom or group selected from the group consisting of monocyclic, bicyclic or tricyclic heterocycloalkyl groups having 3 to 15 carbon atoms. R4 and R6 or R6 and R9 may be combined to form an unsaturated bond with the existing carbon-carbon bond.
R10 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a monocyclic, bicyclic or tricyclic aryl group having 6 to 20 carbon atoms, an oxygen atom, a nitrogen atom and a sulfur atom. C3-C15 monocyclic, bicyclic or tricyclic heteroaryl group containing 5 heteroatoms, C3-C15 monocyclic, bicyclic or tricyclic cycloalkyl group, and oxygen atom Any one selected from the group consisting of a monocyclic, bicyclic or tricyclic heterocycloalkyl group having 3 to 15 carbon atoms containing 1 to 5 heteroatoms selected from the group consisting of nitrogen and sulfur atoms Or a single atom or group.
B is a base.   The curing agent for an episulfide compound according to claim 1, wherein in the general formula (1), R4, R5, R6, R7, R8, and R9 are all hydrogen atoms and R10 is a methyl group.   The episulfide compound according to claim 1 or 2, wherein the episulfide compound is an episulfide compound having an episulfide equivalent of 50 to 2,000.   A curable composition comprising the episulfide compound curing agent according to claim 1 and an episulfide compound.   A cured product of an episulfide compound, wherein the episulfide compound is cured with the episulfide compound curing agent according to any one of claims 1 to 3. A method for curing an episulfide compound, wherein the episulfide compound is cured with a compound represented by the following general formula (1).

In general formula (1),
X ₁ , X ₂ , and X ₃ are each independently any one selected from the group consisting of a hydrogen atom, an oxygen atom, an alkylene group having 1 to 3 carbon atoms, a sulfur atom, a sulfonyl group, and a silanol group. An atom or group.
R1, R2, and R3 are each independently a group consisting of an alkyl group having 1 to 20 carbon atoms, a monocyclic, bicyclic or tricyclic aryl group having 6 to 20 carbon atoms, an oxygen atom, a nitrogen atom, and a sulfur atom. A monocyclic, bicyclic or tricyclic heteroaryl group having 3 to 15 carbon atoms containing 1 to 5 heteroatoms selected from: a monocyclic, bicyclic or tricyclic cyclocarbon having 3 to 15 carbon atoms An alkyl group and a monocyclic, bicyclic or tricyclic heterocycloalkyl group having 3 to 15 carbon atoms and containing 1 to 5 heteroatoms selected from the group consisting of oxygen, nitrogen and sulfur atoms Any one group selected from the group. Two or more groups selected from the group consisting of R1, R2, and R3 may be bonded to form a cyclic structure, and the cyclic structure is selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom. 1 or 2 or more heteroatoms may be present in the ring. However, when X ₁ , X ₂ , and X ₃ are hydrogen atoms or silanol groups, R1, R2, and R3 are not present.
R4, R5, R6, R7, R8, and R9 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a silanol group, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 6 to 20 carbon atoms. A monocyclic, bicyclic or tricyclic ring having 3 to 15 carbon atoms containing 1 to 5 heteroatoms selected from the group consisting of monocyclic, bicyclic or tricyclic aryl groups, oxygen atoms, nitrogen atoms and sulfur atoms 1 to 5 heteroatoms selected from the group consisting of a heteroaryl group of the formula, a monocyclic, bicyclic or tricyclic cycloalkyl group having 3 to 15 carbon atoms, and an oxygen atom, a nitrogen atom and a sulfur atom. It is any one atom or group selected from the group consisting of monocyclic, bicyclic or tricyclic heterocycloalkyl groups having 3 to 15 carbon atoms. R4 and R6 or R6 and R9 may be combined to form an unsaturated bond with the existing carbon-carbon bond.
R10 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a monocyclic, bicyclic or tricyclic aryl group having 6 to 20 carbon atoms, an oxygen atom, a nitrogen atom and a sulfur atom. C3-C15 monocyclic, bicyclic or tricyclic heteroaryl group containing 5 heteroatoms, C3-C15 monocyclic, bicyclic or tricyclic cycloalkyl group, and oxygen atom Any one selected from the group consisting of a monocyclic, bicyclic or tricyclic heterocycloalkyl group having 3 to 15 carbon atoms containing 1 to 5 heteroatoms selected from the group consisting of nitrogen and sulfur atoms Or a single atom or group.
B is a base.